Fe-cr-al based alloy foil and method for producing the same

ABSTRACT

The present invention provides an Fe—Cr—Al-based alloy for catalyst carriers and a foil thereof having a thickness of 40 μm or less, the alloy and the foil improved in the oxidation resistance at high temperatures and having excellent deformation resistance.  
     Specifically, the present invention provides an Fe—Cr—Al-based alloy foil and a manufacturing method thereof, comprising 16.0 to 25.0 mass % of Cr, 1 to 8 mass % of Al, La, Zr, and the balance being Fe and incidental impurities. The contents by mass % of La and Zr meet the following ranges when the foil thickness thereof is t μm: 
     1.4/ t≦La ≦6.0/ t   (1) 
     0.6/ t≦Zr ≦4.0/ t   (2) 
     The Fe—Cr—Al-based alloy foil may further comprises Hf and the balance being Fe and incidental impurities, wherein the contents by mass % of La, Zr, and Hf meet the following ranges: 
     1.4/ t≦La ≦6.0/ t   (1) 
     0.4/ t≦Zr ≦2.0/ t   (3) 
     0.5/ t≦Hf ≦2.0/ t   (4)

[0001] The present invention relates to an Fe—Cr—Al-based alloy foil having oxidation and deformation resistances at high temperatures and to a manufacturing method thereof. The alloy foil is suitable for catalytic converters for automotive exhaust gas purification, where the catalyst carriers and the catalytic converters are exposed to intense vibration and thermal shock in a high-temperature oxidizing atmosphere. The alloy foil is also useful for devices and apparatuses for combustion gas exhaust systems.

BACKGROUND ART

[0002] Replacing conventional ceramic catalytic converter carriers for automotive exhaust gas purification apparatuses with a metal honeycomb as disclosed in Japanese unexamined patent publication No. 56-96726 facilitates the miniaturization of catalytic converters and improves engine performance.

[0003] In view of environmental protection, it is required that automotive exhaust gas purification apparatuses be capable of starting a catalytic reaction immediately after the engine is started. A catalytic converter of the apparatus is located as near the combustion environment as possible so that high temperature exhaust gas can immediately reach the converter, and thus the catalytic converter reaches a catalytic activation temperature in a short period. In this case, the catalytic converter is exposed to thermal cycles of heating and cooling in a high-temperature range and engine judders, that is, it has been used in severe conditions. Ceramics conventionally used as a material for the catalytic converters is not suitable for practical use because they are easily damaged by thermal shock. Thus, oxidation-resistant metals such as Fe—Cr—Al-based alloys are used. An Fe—Cr—Al-based alloy exhibits oxidation resistance at high temperatures because easily oxidizable Al is oxidized prior to Fe to form an oxide film of Al₂O₃ which protects the alloy surface from the oxidation. After the consumption of Al in the alloy, Cr is preferentially oxidized at the interface between the Al₂O₃ oxide film and the alloy. Such Fe—Cr—Al-based alloys are disclosed in Japanese unexamined patent publication Nos. 56-96726 (mentioned above), 7-138710, 9-279310, etc.

[0004] As mentioned above, emission control is strengthened in view of environmental protection, the demand that exhaust gas be purified from the beginning of the engine start has been intensifying in these years. In order to comply with the control, the use of a metal carrier has been increasing, and the demand for thin foil thereof is intensifying. This is because a reduction in the wall thickness of the metal carrier allows exhaust back pressures to be reduced and allows the catalyst to be activated in a short period due to decreased heat capacity. However, the reduced foil thickness requires that materials for the foil be higher oxidation resistant. Also, since the reduced foil thickness leads to deformation by heat, deformation resistance at high temperatures (less elongation at high temperatures and less fracture due to heat stress) is further required.

[0005] Conventional Fe—Cr—Al-based alloys have a deformation problem at high temperatures and improved oxidation resistance is required to help to improve the durability thereof. The present invention is intended to provide an Fe—Cr—Al-based alloy for catalyst carriers and a foil thereof having a thickness of 40 μm or less, the alloy and the foil improved in the oxidation resistance at high temperatures and having excellent deformation resistance. The material of the present invention is specifically suitable for catalytic converter materials and for instruments and apparatuses in combustion gas exhaust systems.

DISCLOSURE OF INVENTION

[0006] The inventors have found that the effective content of La depends on the foil thickness through close examinations of the contents of La, Zr, and Hf, the initial oxidation resistance, and the deformation resistance at high temperatures. The inventors reached a result that the thinner the foil thickness is, the more remarkable the effect is, and thus the present invention was completed.

[0007] A first invention is an Fe—Cr—Al-based alloy foil comprising 0.07 mass % or less of C, 0.5 mass % or less of Si, 0.5 mass % of Mn, 16.0 to 25.0 mass % of Cr, 1 to 8 mass % of Al, 0.05 mass % or less of N, La, Zr, and the balance being Fe and incidental impurities. The contents by mass % of La and Zr meet the following ranges when the foil thickness thereof is t μm:

1.4/t≦La≦6.0/t  (1)

0.6/t≦Zr≦4.0/t  (2)

[0008] A second invention is the Fe—Cr—Al-based alloy foil according to the first invention, further comprising Hf and the balance being Fe and incidental impurities, wherein the contents by mass % of La, Zr, and Hf meet the following ranges:

1.4/t≦La≦6.0/t  (1)

0.4/t≦Zr≦2.0/t  (3)

0.5/t≦Hf≦2.0/t  (4)

[0009] A third invention is the Fe—Cr—Al-based alloy foil according to the first or the second inventions in which the final foil thickness is preferably 40 μm or less. A fourth invention is the Fe—Cr—Al-based alloy foil according to the first, the second, or third invention, further comprising lanthanoids other than La and Ce such that the contents thereof are each 0.001 to 0.05 mass % and totally 0.2 mass % or less. Such an alloy foil has excellent characteristics.

[0010] A fifth invention is a favorable Fe—Cr—Al-based alloy foil according to the first to fourth inventions, in which the completed foil preferably has a structure of which the mean crystal grain size is 5 μm or less or a rolling structure. A sixth invention is a method of manufacturing an Fe—Cr—Al based alloy foil. The manufacturing method comprises preparing a molten steel comprising 0.07 mass % or less of C, 0.5 mass % or less of Si, 0.5 mass % of Mn, 16.0 to 25.0 mass % of Cr, 1 to 8 mass % of Al, 0.05 mass % or less of N, La, Zr, and the balance being Fe and incidental impurities in a molten state. The method also comprises: pouring the molten steel to a slab is comprised; perform hot rolling; perform annealing; and repeating cold rolling and annealing to form a foil. In this instance, the contents by mass % of La and Zr meet the following ranges when the foil thickness thereof is t μm:

1.4/t≦La≦6.0/t  (1)

0.6/t≦Zr≦4.0/t  (2)

[0011] A seventh invention is the manufacturing method of an Fe—Cr—Al-based alloy foil according to the sixth invention, in which the molten steel further comprises Hf and the contents by mass % of La, Zr, and Hf meet the following ranges:

1.4/t≦La≦6.0/t  (1)

0.4/t≦Zr≦2.0/t  (3)

0.5/t≦Hf≦2.0/t  (4)

[0012] An eighth invention is the manufacturing method of an Fe—Cr—Al-based alloy foil according to the sixth or seventh invention, in which annealing before the final cold rolling is performed at a temperature of 700 to 1000° C.

[0013] In the manufacturing method of the Fe—Cr—Al-based alloy foil of the present invention, the annealing before the final cold rolling is performed at a temperature of 700 to 1000° C. in the foil production process.

BRIEF DESCRIPTION OF THE DRAWINGS

[0014]FIG. 1 is a graph showing the relationship between La content and the oxidation resistance at various foil thicknesses.

[0015]FIG. 2 is a graph showing the relationship between Zr content and the oxidation and the deformation resistances of foil containing 0.06 mass % of La at various thicknesses.

[0016]FIG. 3 is a graph showing the relationship between Zr content and the oxidation and the deformation resistances of foil containing 0.06 mass % of La and 0.03 mass % of Hf at various thicknesses.

[0017]FIG. 4 is a graph showing the relationship between Hf content and the oxidation and the deformation resistances of foil containing 0.06 mass % of La and 0.03 mass % of Zr at various thicknesses.

BEST MODE FOR CARRYING OUT THE INVENTION

[0018] An alloy foil of the invention contains especially La and Zr. The foil may further contain Hf. Each component is adequately contained depending on the final foil thickness to improve oxidation and deformation resistances at high temperatures. The following are effects of the components and the reasons for determining the contents.

[0019] Al: 1 to 8 Mass %

[0020] Al is an essential element to ensure the oxidation resistance in the present invention. When the Fe—Cr—Al-based alloy remains at high temperatures, Al is oxidized prior to Fe and Cr to form an oxide film of Al₂O₃ which protects the alloy surface from oxidation, thereby improving the oxidation resistance. If the Al content is less than 1 mass %, a pure Al₂O₃ film cannot be formed, and consequently sufficient oxidation resistance cannot be ensured. The Al content therefore must be 1 mass % or more. Although increasing the Al content is advantageous in view of the oxidation resistance, more than 8 mass % of Al causes cracking and fracturing of plates or the like during hot rolling, thus making manufacturing difficult. The Al content therefore is limited to 8 mass % or less.

[0021] Cr: 16 to 25 Mass %

[0022] Cr contributes to an improvement in the oxidation resistance of Al, and also is itself oxidation resistant. If the Cr content is less than 16.0 mass %, the oxidation resistance cannot be ensured. In contrast, a Cr content of more than 25.0 mass % leads to lowered toughness, thus causing cracking and fracturing of plates during cold rolling. The Cr content is therefore in the range of 16.0 to 25.0 mass %.

[0023] Si: 0.5 Mass % or Less

[0024] Si, as well as Al, is an element which enhances the oxidation resistance of the alloy as in the case of Al, and therefore may be contained in the alloy. However, large Si content leads to lowered toughness. The upper limit of Si content is therefore 0.5 mass %.

[0025] Mn: 0.5 Mass % or Less

[0026] Mn may be contained as an auxiliary agent for the deoxidization of Al. However, a large amount of Mn remaining in the steel lead to decreased oxidation resistance and deteriorated corrosion resistance; hence the Mn content is preferably as low as possible. The Mn content is limited to 0.5 mass % or less in consideration of the industrial and economical ingot technique.

[0027] La, Zr, Hf:

[0028] La, Zr, and Hf are significantly important elements in the present invention. Oxidation of an Fe—Cr—Al-based alloy generally proceeds as follows: First, only an Al₂O₃ film preferentially grows in the early oxidation stage. When Al is completely consumed, this oxidation (hereinafter referred to as the first step) is completed. Next, when Al in the steel is depleted, the second step in which Cr₂O₃ grows between the Al₂O₃ film and the base alloy (hereinafter referred to as the second step) starts. Finally, the production of iron oxides starts, so that a value of weight increase by oxidation rapidly increases. This stage is the third step (hereinafter referred to as the third step).

[0029] Conventionally, in actual environment in which catalyst carriers are used, the oxidation of a foil having a thickness of more than 50 μm is completed at the first step. In contrast, a thinner foil often allows the oxidation to change to the second step relatively early in the actual environment because the absolute amount of Al in the steel is reduced. A foil having a thickness of 40 μm or less requires the oxidation resistance after the second step, which has been unnoticed.

[0030] La contributes to an improvement in the adhesion, to the base metal, of surface-oxidized films such as Al₂O₃ and Cr₂O₃ which are created at high temperature in the Fe—Cr—Al-based alloy and is remarkably effective in improving the oxidation resistance and the peeling resistance of oxidized scale. At the same time, La is also effective in lowering the oxidation rate of Al, hence being an essential element. Adding Zr with La inhibits the consumption of Al, thereby delaying the production times of Al₂O₃ and Cr₂O₃ films. Thus, Zr contributes to an improvement in the oxidation resistance of the alloy. Furthermore, adding Hf with La and Zr particularly inhibits the consumption of Al, thereby delaying the production times of Al₂O₃ and Cr₂O₃ films. Thus, Hf contributes to an improvement in the oxidation resistance of the alloy. At the same time, Hf inhibits the production of a Cr₂O₃ film, thereby reducing the amount of the deformation of the foil, which probably arises from a difference of thermal expansion coefficients between Cr₂O₃ and the base metal. Typically a thin material, such as a honeycomb, having a less elongation barely increases in the heat stress and hardly fractures; hence, it is a long-life material. The less the elongation is, the better it is, and the elongation is preferably about 3% or less.

[0031] According to intensive examination on the contents of La, Zr, and Hf, oxidation resistances thereof, especially the oxidation resistances at high temperatures in the second step, and the elongation, the inventors found that effective contents of La, Zr, and Hf depend on foil thicknesses.

[0032] As an example, the case of La will be described below. La contributes to an improvement in the adhesion, to the base metal, of surface-oxidized films such as Al₂O₃ and Cr₂O₃ which are formed at high temperatures in the Fe—Cr—Al-based alloy, as described above. This action is caused by diffusion of La in the direction of the foil thickness when the alloy is heated to a high temperature. The La content effective in improving the adhesion, to the base metal, of surface-oxidized films such as Al₂O₃ and Cr₂O₃ is probably determined according to unit surface area. Also, the absolute amount of La which diffuses in the direction of the thickness and then reaches the foil surface is probably proportional to the foil thickness. This means that the La content per unit volume must be increased in advance according to the reduced thickness in order to compensate for the amount of La diffusing in the direction of the thickness when heated to a high temperature because it is decreased according to the reduced thickness. This is because the thin thickness is likely to cause a shortage of the absolute amount of La diffusing in the direction of the thickness, so that the adhesion, to the base metal, of surface-oxidized films such as Al₂O₃ and Cr₂O₃ is not improved. However, this does not necessarily mean that the more La content is, the better the result will be. According to the degree of remaining La in the steel, which does not diffuse in the direction of the thickness when heated to a high temperature, La content is limited by itself. This is because if La remains in the steel, La itself is oxidized and this leads to a deterioration in oxidation resistance. FIG. 1 shows a result of a close examination of the relationship between La content (mass %) and the oxidation resistance in a thickness t (μm). This data is a result of a test in which foil specimens were heated in an air of 1200° C. for 150 hours.

[0033] As for the oxidation resistance, the specimens increasing in weight by oxidation by less than 10 g/m² are judged to be favorable. As for the deformation resistance, the specimens elongating by less than 3% in the second step are judged to be favorable. For each specimen exhibiting a favorable result in both the oxidation and the deformation resistances, a white circle is marked; for each specimen exhibiting an inferior result in both the oxidation and the deformation resistances, a black circle is marked; and for each specimen exhibiting a inferior result in only the deformation resistance, a black triangle is marked.

[0034] The La content causing satisfactory oxidation and deformation resistances lies in the region between Curve 1 for La=1.4/t and Curve 2 for La=6.0/t. According to FIG. 1, when the La content (mass %) is 1.4/t or more at a foil thickness t (μm), the oxidation resistance is favorable, and when the La content is 6.0/t or less, the elongation can be lowered in the second step. The La content of the present invention therefore is determined to be within the range meeting the following relational expression.

1.4/t≦La≦6.0/t  (1)

[0035] Next, Zr and Hf contents are described below. When La and Zr are added, the following relational expression must be met.

0.6/t≦Zr≦4.0/t  (2)

[0036] When La, Zr, and Hf are added, the following relational expressions must be met.

0.4/t≦Zr≦2.0/t  (3)

0.5/t≦Hf≦2.0/t  (4)

[0037] The inventors examined the diffusion behaviors of Hf and Zr in the oxidation steps, the components added together with La. The inventors found that when the foil is heated, Zr and Hf diffuse toward the interface between the Al₂O₃ film of the foil surface and the base metal in the early oxidation stage, and subsequently settle in the Al₂O₃ grain boundary of the Al₂O₃ film of the foil surface. Also, the inventors found that Zr and Hf settling in the grain boundary inhibit oxygen from diffusing into Al₂O₃ and Al₂O₃ from growing. The inventors further found that Hf and Zr settling in the Al₂O₃ grain boundary inhibit Cr₂O₃ from growing and decreases the oxidation rate in the second step. Although the reason is not yet clear, the inventors have found that Hf is more easily settled in the Al₂O₃ grain boundary than Zr is, and that adding Zr together with Hf is more effective than adding only Zr. The inventors also have found that when Hf and Zr are added in combination, Hf diffuses toward the Al₂O₃ grain boundary. The amount of Zr diffusing toward the Al₂O₃ grain boundary, therefore, must be lowered compared with the case of only Zr; otherwise, Zr would become oxides in the Al₂O₃ grain boundary and the oxidation resistance of the overall foil would be decreased.

[0038] As for the effect of the combination use of Zr and Hf on the oxidation resistance, when the contents of Zr and Hf are too low, they do not settle in the Al₂O₃ grain boundary in the early oxidation stage, so that the oxidation resistance is not adequately exhibited. In contrast, when the contents of Zr and Hf are significantly high, they are concentrated not only in the Al₂O₃ grain boundary but also at the interface between the scale and the base metal, and become oxides. The oxides serve as short-cut passages for oxygen. Thus, the oxidation rate is increased, and the oxidation resistance is decreased. In particular, this deterioration of the oxidation resistance becomes more severe in the second step, and at this time the elongation increases. The adequate amount depends on the surface area of oxidation, hence depending on the foil thickness. The reason is exactly the same as the reason described on La.

[0039]FIG. 2 shows the relationship between Zr content and the oxidation resistance of foil containing 0.06 mass % of La of various thicknesses. This data is a result of a test in which foil specimens were heated in an air of 1200° C. for 150 hours.

[0040] As for the oxidation resistance, the specimens increasing in weight by oxidation by less than 10 g/m² are judged to be favorable. As for the deformation resistance, the specimens elongating by less than 3% in the second step are judged to be favorable. For each specimen exhibiting favorable oxidation and deformation resistances, a white circle is marked; for each specimen exhibiting inferior oxidation and deformation resistances, a black circle is marked; and for each specimen exhibiting only inferior deformation resistance, a black triangle is marked. The Zr content causing satisfactory oxidation and deformation resistances lies in the region between Curve 3 for Zr=0.6/t and Curve 4 for Zr=4.0/t.

[0041]FIG. 3 shows the relationship between Zr content and the oxidation resistance of foil containing 0.06 mass % of La and 0.03 mass % of Hf of in various thicknesses. This data is a result of a test in which foil specimens were heated in an air of 1200° C. for 150 hours.

[0042] As for the oxidation resistance, the specimens increasing in weight by oxidation by less than 10 g/m² are judged to be favorable. As for the deformation resistance, the specimens elongating by less than 3% in the second step are judged to be favorable. For each specimen exhibiting favorable oxidation and deformation resistances, a white circle is marked; for each specimen exhibiting inferior oxidation and the deformation resistances, a black circle is marked; and for each specimen exhibiting only inferior deformation resistance, a black triangle is marked. The Zr content causing satisfactory oxidation and deformation resistances lies in the region between Curve 5 for Zr=0.4/t and Curve 6 for Zr=2.0/t.

[0043]FIG. 4 shows the relationship between Hf content and the oxidation and the deformation resistances of foil containing 0.06 mass % of La and 0.03 mass % of Zr of various thicknesses. This data is a result of a test in which foil specimens were heated in an air of 1200° C. for 150 hours.

[0044] As for the oxidation resistance, the specimens increasing in weight by oxidation by less than 8 g/m², by 8 g/m² or more and less than 10 g/m², and by more than 10 g/m² are judged to be most favorable, favorable, and inferior, respectively. As for the deformation resistance, the specimens elongating by less than 3% in the second step are judged to be favorable. For each specimen exhibiting most favorable oxidation and deformation resistances, a double circle is marked; for each specimen exhibiting favorable oxidation and deformation resistances, a white circle is marked; for each specimen exhibiting inferior oxidation and deformation resistances, a black circle is marked; and for each specimen exhibiting only inferior deformation resistance, a black triangle is marked. The Hf content causing satisfactory oxidation and deformation resistances lies in the region between Curve 7 for Hf=0.5/t and Curve 8 for Hf=2.0/t.

[0045] According to FIGS. 1 to 4, preferably the Zr and Hf contents depend on foil thicknesses. When La and Zr are present, the Zr content is preferably within the range of the following relational expression:

0.6/t≦Zr≦4.0/t  (2).

[0046] When La, Zr, and Hf are present, the Zr and Hf contents are preferably within the range of the following relational expressions:

0.4/t≦Zr≦2.0/t  (3), and

0.5/t≦Hf≦2.0/t  (4).

[0047] Thus, excellent oxidation resistance and less elongation (a deformation resistance) are exhibited. The contents of Zr and Hf therefore are specified as follows:

[0048] When La and Zr are present,

0.6/t≦Zr≦4.0/t  (2).

[0049] When La, Zr, and Hf are present,

0.4/t≦Zr≦2.0/t  (3) and

0.5/t≦Hf≦2.0/t  (4).

[0050] C: 0.07 Mass % or Less

[0051] Excess content of C leads to decreased temperature strength, and also to decreased oxidation resistance and lowered toughness. The C content therefore is limited to 0.07 mass % or less.

[0052] N: 0.05 Mass % or Less

[0053] Excess content of N leads to lowered toughness in the same manner as C, and also causes cracking during cold rolling. Thus, the manufacturing becomes difficult and product workability is lowered. Also, if N reacts with Al and coarse AlN is precipitated, the oxidation resistance is decreased.

[0054] N content therefore is limited to 0.05 mass % or less.

[0055] Lanthanoids Other Than La and Ce: 0.001 to 0.05 Mass % Each and 0.2 Mass % or Less in Total

[0056] Lanthanoids consist of fifteen metal elements having an atomic numbers from 57 to 71, such as La, Ce, and Nd, etc. Lanthanoids other than La and Ce improve the adhesion of oxide films produced on the foil surface, such as Al₂O₃ and Cr₂O₃, thereby contributing to an improvement in the oxidation resistance. Ce is excluded because it deteriorates the toughness, so that the plate easily cracks during hot rolling. Furthermore, Ce significantly lowers the oxidation resistance. Since La is generally contained together with other lanthanoids except Ce rather than purified from raw ore, the contents of lanthanoids except La and Ce can be each in the range of 0.001 to 0.05 mass %. To prevent the plate from cracking during hot rolling, the total content of lanthanoids except La and Ce is determined to be 0.2 mass % or less.

[0057] The components of the foil of the present invention are prepared in a molten state and poured on a steel ingot or a slab. After hot rolling and annealing, cold rolling and annealing are repeated so that a foil having a desired thickness of 40 μm or less is formed. The foil is wound on a coil. The annealing before the final rolling is performed at a temperature of 700 to 1000° C. This is because the inventors found that elemental La, Zr, Hf, and the like, which are main points of the invention, do not necessarily diffuse sufficiently and can localize in, for example, planar flow casting or the like, and that each element does not constantly exhibit the effects arising from meeting the relational expressions of the foil thickness.

[0058] In addition, if planar flow casting or the like is performed in a mass production, variations in product quality are exhibited wherein one part has a preferable oxidation resistance, while another does not. This is because rapid cooling in planar flow casting allows a part having a structure or a component which, on the basis of the phase diagram, are not expected to be formed. Thus, depending on the manufacturing method, some parts may have completely different characteristics; hence specified components do not necessarily result in a uniform oxidation-resistant foil because of the effect of variations of manufacturing conditions. Furthermore, the inventors found that it is effective to perform the annealing at a temperature of 700 to 1000° C. before the final cold rolling. This is because the elements do not sufficiently diffuse at temperatures of less than 700° C.; the thickness of the oxidized film of the surface increases at a temperature of more than 1000° C.; and thus descaling becomes difficult. The temperature for the annealing before the final cold rolling therefore is determined to be 700 to 1000° C., and preferably 800 to 950° C.

[0059] The annealing is preferably performed in a reducing atmosphere such as in ammonia cracked gas.

[0060] Preferably, the structure of a completed foil of the present invention has a mean crystal grain size of 5 μm or less or a rolling structure (meaning that the crystal has not been recrystallized by the final annealing but is in its natural state as rolled, hereinafter referred to as rolling structure). If the completed foil has a large crystal grain size or a columnar structure before being incorporated in a honeycomb, large deformation of the foil is caused during oxidation. In particular, the foil having a thickness of 40 μm or less causes Cr to be oxidized in the second step, thereby bringing about still larger deformation supposedly arising from a difference of thermal expantion coefficients between chromium oxide and the base metal. However, if the foil structure has a mean crystal grain size of 5 μm or less or a rolling structure, foil shrinkage is caused by a deflection arising from a rolling force. The shrinkage is minimized in an oxidation stage progressed a certain degree and then the foil is expanded again. Thus, the smaller the initial structure of the foil is, the less the expansion rate is with respect to the size of the initial structure. This effect is exhibited in the case of a mean crystal grain size of 5 μm or less, and is especially remarkable in the rolling structure case. If the mean crystal grain size is more than 5 μm, the foil is expanded from the beginning of oxidation. The foil structure preferably has a mean crystal grain size of 5 μm or less or a rolling structure.

[0061] Also, the present invention is preferably applied to foils intended for use in completed products having a thickness of 40 μm or less. The foil having a thickness of 40 μm or less, more specifically 35 μm, is effective in that an exhaust back pressure is reduced by reducing the wall thickness of the metal carrier and that the temperature rises in a short period after engine start and rapidly reaches a temperature capable of activating a catalyst owing to the reduced heat capacity. It goes without saying that even foils having a thickness of more than 40 μm are oxidation resistant and are effective against the deformation in the second step as far as the compositions are within the description of the present invention. Nevertheless, having a thickness of 40 μm or less is remarkably effective in rapidly raising the temperature. The thickness is therefore preferably 40 μm or less, and more preferably 35 μm or less.

EXAMPLE 1

[0062] Tables 1 and 2 show the compositions of specimens. These materials were formed into ingots by vacuum melting. After being heated to 1200° C., each ingot was hot-rolled to be formed into a plate 3 mm thick at a temperature of 1200 to 900° C. Then, after annealing at 950° C., cold rolling and annealing were repeated until a foil 0.1 mm thick was formed. The foil was annealed at 900° C. for 1 min in ammonia cracked gas, and finally was cold-rolled to be formed into a foil having a thickness of 20 to 40 μm. Each foil specimen has a rolling structure.

[0063] Each foil specimen (50 mm×50 mm of rectangular foil) prepared as above was oxidized in air at 1100° C. for 500 hours and the oxidation resistance characteristics thereof were examined. Results are shown in Tables 3, 4, and 5. Corresponding to experimental run numbers 1 to 20 in Table 1, Table 3 shows results of the experiments in which La and Zr were added. The relationships between La and Zr contents each and the foil thickness in Table 3 are represented by left and right side values of the following expressions, respectively.

1.4/t≦La≦6.0/t  (1)

0.6/t≦Zr≦4.0/t  (2)

[0064] Corresponding to experimental run numbers 21 to 40 in Table 2, Table 4 and 5 show results of the experiments in which La, Zr, and Hf were added. The relationships between La and Zr contents each and the foil thickness in Table 4 are represented by left and right side values of the following expressions, respectively.

1.4/t≦La≦6.0/t  (1)

0.4/t≦Zr≦2.0/t  (3)

0.5/t≦Hf≦2.0/t  (4)

[0065] In tables 3 and 5, weight increase, thermal expantion coefficients, and observed oxides are shown. As for weight increase, a double circle, a white circle, a triangle, or a cross is marked for each specimen which increased in weight at ambient temperature after air cooling by less than 5.0 g/m², 5.0 g/m² or more and less than 8.0 g/m², 8.0 g/m² or more and less than 10.0 g/m², or otherwise, respectively. As for thermal expantion coefficients, a double circle, a white circle, a triangle, or a cross is marked for each specimen of which a side length (50 mm) expanded after complete cooling by less than 1.0%, 1.0% or more and less than 2.0%, 2.0% or more and less than 3.0%, or 3.0% or more, respectively. Specimens exhibiting an expansion rate of less than 3.0% are judged to be acceptable. Observed oxides are oxides which were observed by an X-ray diffraction analysis after the oxidation test.

[0066] Steels within the description of the present invention having contents according to the foil thickness exhibited most favorable oxidation resistance. Furthermore, even in the case of a foil thickness of 40 μm or less, favorable oxidation resistance was exhibited. Even though specimens contained the same components, test results differed according to the foil thicknesses. In particular, when the La, Zr, and Hf contents were not specified for thin foils, the oxidation resistance decreased. Also, the elongation in the second step, which is important for foils having a thickness of 40 μm or less, was favorable. According to the results of X-ray diffraction analysis, steels containing an excess amount of any of La, Zr, and Hf with respect to the relational expressions deteriorated in the oxidation resistance, and particularly in the second step, because these elements resulted in oxides. Accordingly, the foil of the present invention is suitable for a material for catalytic converters requiring a most favorable oxidation resistance.

EXAMPLE 2

[0067] Table 6 shows compositions for test materials. Part of each composition was formed into an ingot by vacuum melting. After being heated to 1200° C., the ingot was hot-rolled to be formed into a plate 3 mm thick at a temperature of 1200 to 900° C. Then, after annealing at 950° C., cold rolling and annealing were repeated, so that a foil 0.1 mm thick was formed. The foil was annealed in ammonia cracked gas under the condition shown in Table 8, and finally was cold-rolled to be formed into a foil having a thickness of 20 to 40 μm. In addition, another part of the composition was provided with a finishing anneal in ammonia cracked gas so as resulting in a specimen having a structure with a different crystal grain size, and was used for the oxidation test. Still another part was formed into a foil having a predetermined thickness of 20 to 40 μm by planar flow casting and was used for the oxidation test. Each specimen was a rectangular foil with 50 mm×50 mm. The relationships between La, Zr, and Hf contents each and the foil thickness are represented by left and right side values of the following expressions, respectively.

1.4/t≦La≦6.0/t  (1)

0.4/t≦Zr≦2.0/t  (3)

0.5/t≦Hf≦2.0/t  (4)

[0068] The specimens with various thicknesses each was used for the oxidation test at 1100° C. for 500 hours. Results are shown in Table 8. Table 8 shows conditions where the specimens were annealed before the final rolling, structures or mean crystal grain sizes of completed foil products, oxidation increase values, and thermal expantion coefficients. The mean crystal grain size was obtained by an image analysis in accordance with JIS G0552 in which the structure in the section perpendicular to the rolling direction was observed with a microscope. In addition, planar flow cast ribbons are described in the table as comparative examples. As for weight increase, a double circle, a white circle, a triangle, or a cross is marked for each specimen which increased in weight at ambient temperature after air cooling by less than 5.0 g/m², 5.0 g/m² or more and less than 8.0 g/m², 8.0 g/m² or more and less than 10.0 g/m², or otherwise, respectively. As for thermal expantion coefficients, a double circle, a white circle, a triangle, or a cross is marked for each specimen of which the longitudinal side length expanded after complete cooling by less than 1.0%, 1.0% or more and less than 2.0%, 2.0% or more and less than 3.0%, or 3.0% or more, respectively. Specimens exhibiting an expansion rate of less than 3.0% were judged to be acceptable.

[0069] Steels annealed before the final rolling as described in the present invention exhibit more favorable oxidation resistance. Furthermore, even in the case of a foil thickness of 40 μm or less, favorable oxidation resistance is exhibited. Even though specimens contain the same components, the oxidation resistance of specimens formed by repeated annealing is far more favorable than that of specimens formed by planar flow casting. While the specimens formed by planar flow casting are each partly more oxidation resistant than the specimens formed by hot rolling after casting and repeating annealing and cold rolling, they are not partly oxidation resistant and exhibit ununiform oxidation resistance in a foil. In addition, forming a foil of which the final crystal has a structure as described in the present invention allows the expansion rate to decrease. Accordingly, the foil of the present invention is suitable for a material for catalytic converters requiring a most favorable oxidation resistance.

[0070] Industrial Applicability

[0071] According to the present invention, an Fe—Cr—Al-based alloy containing La, Zr, and/or Hf according to the foil thickness thereof can result in a oxidation and deformation resistant alloy foil. The alloy of the present invention is suitable for a material for catalytic converters of automobiles, and more specifically the alloy formed into a foil having a thickness of 40 μm or less has excellent characteristics. TABLE 1 Component (wt%) Experiment Steel Lanthanoids except No. No. C Si Mn Cr Al N La Zr Hf La and Ce  1 A 0.005 0.10 0.10 20.2 5.8 0.004 0.052 0.025 —  2 B 0.010 0.20 0.20 18.5 7.9 0.005 0.085 0.032 —  3 C 0.025 0.22 0.09 20.3 5.6 0.004 0.069 0.050 —  4 D 0.015 0.50 0.16 22.3 6.0 0.008 0.065 0.026 — Nd = 0.01, Sm = 0.05  5 E 0.010 0.30 0.20 20.5 3.0 0.007 0.058 0.018 —  6 F 0.008 0.22 0.09 20.2 4.8 0.004 0.098 0.036 —  7 G 0.028 0.25 0.16 24.5 5.5 0.008 0.065 0.045 — Sm = 0.01  8 H 0.007 0.20 0.20 16.5 6.2 0.005 0.125 0.120 —  9 I 0.035 0.22 0.09 20.1 5.5 0.008 0.058 0.025 — Nd = 0.01 10 J 0.015 0.10 0.16 19.5 6.2 0.008 0.158 0.034 — Sm = 0.01 11 K 0.010 0.30 0.20 21.2 5.6 0.010 0.085 0.136 — 12 L 0.025 0.10 0.09 18.5 5.6 0.004 0.039 0.025 — 13 M 0.015 0.50 0.16 19.8 6.0 0.008 0.056 0.068 — 14 N 0.010 0.10 0.20 20.3 4.5 0.012 0.172 0.052 — 15 O 0.025 0.22 0.09 22.1 5.5 0.008 0.092 0.031 — 16 A 0.005 0.10 0.10 20.2 5.8 0.004 0.052 0.025 — 17 E 0.010 0.30 0.20 20.5 3.0 0.007 0.058 0.018 — 18 K 0.010 0.30 0.20 21.2 5.6 0.010 0.085 0.136 — 19 P 0.010 0.20 0.20 18.5 7.9 0.005 0.210 0.032 — Nd = 0.01 20 Q 0.025 0.22 0.09 22.1 5.5 0.008 0.092 0.175 —

[0072] TABLE 2 Component (wt%) Experiment Steel Lanthanoids except No. No. C Si Mn Cr Al N La Zr Hf La and Ce 21 R 0.004 0.16 0.10 21.0 5.8 0.005 0.065 0.021 0.025 22 S 0.008 0.12 0.20 19.5 7.8 0.006 0.058 0.035 0.023 23 T 0.015 0.15 0.09 16.5 6.5 0.007 0.185 0.023 0.038 24 U 0.023 0.26 0.16 21.3 5.2 0.012 0.075 0.033 0.035 Nd = 0.01, Sm = 0.05 25 V 0.030 0.25 0.20 18.9 3.0 0.008 0.128 0.050 0.052 26 W 0.008 0.16 0.09 19.8 5.6 0.005 0.056 0.032 0.065 27 U 0.005 0.21 0.16 24.2 5.9 0.004 0.065 0.067 0.030 28 X 0.003 0.35 0.20 18.9 5.6 0.006 0.085 0.015 0.025 Sm = 0.01 29 Y 0.012 0.50 0.09 16.2 6.2 0.007 0.092 0.045 0.062 30 Z 0.007 0.12 0.16 20.2 5.8 0.009 0.156 0.031 0.029 Nd = 0.01 31 AA  0.008 0.13 0.20 20.3 6.0 0.010 0.112 0.018 0.015 Sm = 0.01 32 AB  0.012 0.15 0.09 18.5 4.8 0.012 0.045 0.025 0.052 33 AC  0.016 0.25 0.16 21.5 6.5 0.007 0.098 0.045 0.035 34 AD  0.008 0.12 0.20 22.2 4.3 0.011 0.076 0.054 0.025 35 AE  0.025 0.13 0.09 19.4 5.6 0.008 0.082 0.062 0.037 36 T 0.015 0.15 0.09 16.5 6.5 0.007 0.185 0.023 0.038 37 X 0.003 0.35 0.20 18.9 5.6 0.006 0.085 0.015 0.025 38 AA  0.008 0.13 0.20 20.3 6.0 0.010 0.112 0.018 0.015 39 Y 0.012 0.50 0.09 16.2 6.2 0.007 0.092 0.045 0.062 Nd = 0.01 40 AE  0.025 0.13 0.09 19.4 5.6 0.008 0.082 0.062 0.037

[0073] TABLE 3 Foil La Zr Experiment thickness Left Right Left Right Wt. by Expansion No. (μm) side of (1) side of (1) side of (2) side of (2) oxidation rate Observed oxides Remark  1 30 0.047 0.200 0.020 0.133 ∘ ∘ α-Al₂O₃, Cr₂O₃ Example  2 39 0.036 0.154 0.015 0.103 ∘ ⊚ α-Al₂O₃, Cr₂O₃ Example  3 21 0.067 0.286 0.029 0.190 ∘ ∘ α-Al₂O₃, Cr₂O₃ Example  4 27 0.052 0.222 0.022 0.148 ∘ ∘ α-Al₂O₃, Cr₂O₃ Example  5 50 0.040 0.171 0.017 0.114 ∘ ∘ α-Al₂O₃, Cr₂O₃ Example  6 30 0.047 0.200 0.020 0.133 ∘ ∘ α-Al₂O₃, Cr₂O₃ Example  7 25 0.056 0.240 0.024 0.160 ∘ ∘ α-Al₂O₃, Cr₂O₃ Example  8 29 0.048 0.207 0.021 0.138 ∘ ∘ α-Al₂O₃, Cr₂O₃ Example  9 31 0.045 0.194 0.019 0.129 ∘ ∘ α-Al₂O₃, Cr₂O₃ Example 10 25 0.056 0.240 0.024 0.160 ∘ ∘ α-Al₂O₃, Cr₂O₃ Example 11 26 0.054 0.231 0.023 0.154 ∘ ∘ α-Al₂O₃, Cr₂O₃ Example 12 38 0.037 0.158 0.016 0.105 ∘ ⊚ α-Al₂O₃, Cr₂O₃ Example 13 35 0.040 0.171 0.017 0.114 ∘ ⊚ α-Al₂O₃, Cr₂O₃ Example 14 33 0.042 0.182 0.018 0.121 ∘ ∘ α-Al₂O₃, Cr₂O₃ Example 15 26 0.054 0.231 0.023 0.154 ∘ ∘ α-Al₂O₃, Cr₂O₃ Example 16 25 0.056 0.240 0.024 0.160 Δ Δ α-Al₂O₃, Cr₂O₃ Comparative Example 17 28 0.050 0.214 0.021 0.143 x Δ α-Al₂O₃, Cr₂O₃ Comparative Example 18 36 0.039 0.167 0.017 0.111 x x α-Al₂O₃, Cr₂O₃, ZrO₂ Comparative Example 19 30 0.047 0.200 0.020 0.133 ∘ x α-Al₂O₃, Cr₂O₃, La_(2O) ₃ Comparative Example 20 25 0.056 0.240 0.024 0.160 x x α-Al₂O₃, Cr₂O₃, ZrO₂ Comparative Example

[0074] TABLE 4 Foil La Zr Hf Experiment thickness Left side Right side Left side Right side Left side Right side No. (μm) of (3) of (3) of (4) of (4) of (5) of (5) 21 30 0.047 0.200 0.013 0.067 0.017 0.067 22 45 0.036 0.154 0.010 0.051 0.013 0.051 23 21 0.067 0.286 0.019 0.095 0.024 0.095 24 27 0.052 0.222 0.015 0.074 0.019 0.074 25 35 0.040 0.171 0.011 0.057 0.014 0.057 26 30 0.047 0.200 0.013 0.067 0.017 0.067 27 25 0.056 0.240 0.016 0.080 0.020 0.080 28 35 0.040 0.171 0.011 0.057 0.014 0.057 29 25 0.056 0.240 0.016 0.080 0.020 0.080 30 25 0.056 0.240 0.016 0.080 0.020 0.080 31 39 0.036 0.154 0.010 0.051 0.013 0.051 32 38 0.037 0.158 0.011 0.053 0.013 0.053 33 35 0.040 0.171 0.011 0.057 0.014 0.057 34 33 0.042 0.182 0.012 0.061 0.015 0.061 35 26 0.054 0.231 0.015 0.077 0.019 0.077 36 35 0.040 0.171 0.011 0.057 0.014 0.057 37 25 0.056 0.240 0.016 0.080 0.020 0.080 38 30 0.047 0.200 0.013 0.067 0.017 0.067 39 35 0.040 0.171 0.011 0.057 0.014 0.057 40 38 0.037 0.158 0.011 0.053 0.013 0.053

[0075] TABLE 5 Wt. Experimen by Expansion No. oxidation rate Observed oxides Remark 21 ⊚ ⊚ α-Al₂O₃, Cr₂O₃ Example 22 ⊚ ⊚ α-Al₂O₃ Example 23 ⊚ ⊚ α-Al₂O₃, Cr₂O₃ Example 24 ⊚ ⊚ α-Al₂O₃, Cr₂O₃ Example 25 ⊚ ⊚ α-Al₂O₃ Example 26 ⊚ ⊚ α-Al₂O₃, Cr₂O₃ Example 27 ⊚ ⊚ α-Al₂O₃, Cr₂O₃ Example 28 ⊚ ⊚ α-Al₂O₃, Cr₂O₃ Example 29 ⊚ ⊚ α-Al₂O₃, Cr₂O₃ Example 30 ⊚ ⊚ α-Al₂O₃, Cr₂O₃ Example 31 ⊚ ⊚ α-Al₂O₃, Cr₂O₃ Example 32 ⊚ ⊚ α-Al₂O₃ Example 33 ⊚ ⊚ α-Al₂O₃ Example 34 ⊚ ⊚ α-Al₂O₃, Cr₂O₃ Example 35 ⊚ ⊚ α-Al₂O₃, Cr₂O₃ Example 36 ∘ x α-Al₂O₃, Cr₂O₃ Comparative La₂O₃ example 37 x Δ α-Al₂O₃, Cr₂O₃ Comparative example 38 Δ x α-Al₂O₃, Cr₂O₃ Comparative example 39 x Δ α-Al₂O₃, Cr₂O₃ Comparative HfO₂ example 40 x x α-Al₂O₃, Cr₂O₃ Comparative ZrO₂ example

[0076] TABLE 6 Component Steel Lanthanoids except No. C Si Mn Cr Al N La Zr Hf La and Ce AF 0.005 0.10 0.10 20.2 5.8 0.004 0.071 0.032 0.031 AG 0.007 0.20 0.23 17.8 7.2 0.005 0.085 0.045 0.015 AH 0.012 0.10 0.09 24.8 5.6 0.004 0.058 0.025 0.055 AI 0.003 0.30 0.16 20.5 6.0 0.008 0.115 0.028 0.042 Nd = 0.01

[0077] TABLE 7 Foil La Zr Hf Steel thickness Left side Right side Left side Right side Left side Right side No. (μm) of (3) of (3) of (4) of (4) of (5) of (5) Remark AF 29 0.048 0.207 0.014 0.069 0.017 0.069 Example AG 38 0.037 0.158 0.011 0.053 0.013 0.053 Example AH 25 0.056 0.024 0.016 0.080 0.020 0.080 Example AT 21 0.067 0.286 0.019 0.095 0.024 0.095 Example

[0078] TABLE 8 Anneal before final rolling Finishing anneal Foil Annealing Annealing Structure/ Steel thickness temp. Soaking temp. Soaking mean crystal Wt. increase Expansion Observed No. ingot (μm) (° C.) time (s) (° C.) time (s) grain size Other note by oxidation rate oxides Remark 41 AF 29 900 60 — — Rolling — ⊚ ⊚ α-Al₂O₃ Example 42 550 60 — — Rolling — ∘ ∘ α-Al₂O_(3,) Example Cr₂O₃ 43 850 60  950 60  5 μm — ⊚ ⊚ α-Al₂O₃ Example 44 800 60 1100 60 20 μm — ∘ ∘ α-Al₂O_(3,) Example Cr₂O₃ 45 — — — — Amorphous planar flow Δ x α-Al₂O_(3,) Comparative cast ribbon La₂O₃ Example 46 AG 38 800 150  — — Rolling — ⊚ ⊚ α-Al₂O₃ Example 47 400 30 — — Rolling — ∘ ∘ α-Al₂O_(3,) Example Cr₂O₃ 48 850 60  700 60  2 μm — ⊚ ⊚ α-Al₂O₃ Example 49 900 30 1050 60 15 μm — ∘ ∘ α-Al₂O_(3,) Example Cr₂O₃ 50 — — — — Amorphous planar flow Δ x α-Al₂O_(3,) Comparative cast ribbon Cr₂O₃ Example La₂O₃ 51 AH 25 950 60 — — Rolling — ⊚ ⊚ α-Al₂O₃ Example 52 650 20 — — Rolling — ∘ ∘ α-Al₂O_(3,) Example Cr₂O₃ 53 850 60  920 60  3 μm — ⊚ ⊚ α-Al₂O₃ Example 54 750 50 1000 60  8 μm — ∘ ∘ α-Al₂O_(3,) Example Cr₂O₃ 55 — — — — Amorphous planar flow Δ x α-Al₂O_(3,) Comparative cast ribbon Cr₂O₃ Example La₂O₃ 56 AI 21 750 30 — — Rolling — ⊚ ⊚ α-Al₂O₃ Example 57 600 60 — — Rolling — ∘ ∘ α-Al₂O_(3,) Example Cr₂O₃ 58 950 30  900 60  1 μm — ⊚ ⊚ α-Al₂O₃ Example 59 850 50 1030 60 12 μm — ∘ ∘ α-Al₂O_(3,) Example Cr₂O₃ 60 — — — — Amorphous planar flow Δ x α-Al₂O_(3,) Comparative cast ribbon La₂O₃ Example 

1. An Fe—Cr—Al-based alloy foil comprising 0.07 mass % or less of C, 0.5 mass % or less of Si, 0.5 mass % of Mn, 16.0 to 25.0 mass % of Cr, 1 to 8 mass % of Al, 0.05 mass % or less of N, La, Zr, and the balance being Fe and incidental impurities, wherein the contents by mass % of said La and said Zr meet the following ranges when the foil thickness thereof is t μm: 1.4/t≦La≦6.0/t  (1)0.6/t≦Zr≦4.0/t  (2)
 2. An Fe—Cr—Al-based alloy foil according to claim 1, further comprising Hf and the balance being Fe and incidental impurities, wherein the contents by mass % of said La, said Zr, and said Hf meet the following ranges: 1.4/t≦La≦6.0/t  (1)0.4/t≦Zr≦2.0/t  (3)0.5/t≦Hf≦2.0/t  (4)
 3. An Fe—Cr—Al-based alloy foil according to claim 1 or 2, wherein the foil thickness thereof is 40 μm or less.
 4. An Fe—Cr—Al-based alloy foil according to any one of claims 1 to 3, further comprising lanthanoids other than La and Ce so that the contents thereof are each 0.001 to 0.05 mass % and totally 0.2 mass % or less.
 5. An Fe—Cr—Al-based alloy foil according to any one of claims 1 to 4, wherein a completed foil has a structure of which the mean crystal grain size is 5 μm or less or a rolling structure.
 6. A method of manufacturing an Fe—Cr—Al-based alloy foil, comprising: preparing a molten steel comprising 0.07 mass % or less of C, 0.5 mass % or less of Si, 0.5 mass % of Mn, 16.0 to 25.0 mass % of Cr, 1 to 8 mass % of Al, 0.05 mass % or less of N, La, Zr, and the balance being Fe and incidental impurities in a molten state; pouring the molten steel to a slab; performing hot rolling; performing annealing; and repeating cold rolling and annealing to form a foil, wherein the contents by mass % of said La and said Zr meet the following ranges when the foil thickness thereof is t μm: 1.4/t≦La≦6.0/t  (1)0.6/t≦Zr≦4.0/t  (2)
 7. A method of manufacturing an Fe—Cr—Al-based alloy foil according to claim 6, wherein the molten steel further comprises Hf so that the contents by mass % of said La, said Zr, and said Hf meet the following ranges: 1.4/t≦La≦6.0/t  (1)0.4/t≦Zr≦2.0/t  (3)0.5/t≦Hf≦2.0/t  (4)
 8. A method of manufacturing an Fe—Cr—Al-based alloy foil according to claim 6 or 7, wherein the annealing before the final cold rolling is performed at a temperature of 700 to 1000° C. 